Structure of alkali (alumino) silicate glasses. II. Luminescence of thallium doped sodium aluminosilicates, and implications for optical basicity theories

M. N. Alexander, P. I K Onorato, C. W. Struck, G. W. Tasker, Donald R Uhlmann

Research output: Contribution to journalArticle

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Abstract

Optical excitation and emission spectra are reported for Na aluminosilicate glassed doped with 0.001-0.005 M Tl+ ions, whose spectra probe Na+ environments in the glasses. The experimental data buttress earlier work by the authors, which showed that Al/Na = 1 is the condition for (dis)appearance of nonbridging oxygens in Na aluminosilicate glasses. The Tl+ spectra are in qualitative disagreement with theories of average optical basicity propounded by Jørgensen and by Duffy and Ingram (glass compositions were chosen so samples had theoretical optical basicities of Λth = 0.55, 0.57, or 0.60). In contrast to the single absorption band predicted by average basicity theories, two absorption bands were found for Tl+ in Na aluminosilicate glasses. The two bands arise from Tl+ acting as network modifiers and from Tl+ acting as charge compensators for network Al. The principal features of these spectra are shown to be consistent with XPS results. The assumptions underlying average and group optical basicity theories are critically reviewed and are found to be deficient in that: (1) they direct attention to a network atom (Si or Al) and the oxygen bonded to it, rather than to the luminescent probe ion and its neighboring oxygens; (2) they neglect lattice relaxation (Franck-Condon shift) effects. Important special circumstances are nevertheless identified in which average optical basicity theories may be useful guides to the peak energies of probe ion spectra.

Original languageEnglish (US)
Pages (from-to)63-82
Number of pages20
JournalJournal of Non-Crystalline Solids
Volume91
Issue number1
DOIs
StatePublished - 1987
Externally publishedYes

Fingerprint

Silicates
Thallium
Aluminosilicates
thallium
Alkalies
Alkalinity
Luminescence
alkalies
silicates
Sodium
sodium
luminescence
Glass
glass
ion probes
Ions
Oxygen
Absorption spectra
oxygen
absorption spectra

ASJC Scopus subject areas

  • Ceramics and Composites
  • Electronic, Optical and Magnetic Materials

Cite this

Structure of alkali (alumino) silicate glasses. II. Luminescence of thallium doped sodium aluminosilicates, and implications for optical basicity theories. / Alexander, M. N.; Onorato, P. I K; Struck, C. W.; Tasker, G. W.; Uhlmann, Donald R.

In: Journal of Non-Crystalline Solids, Vol. 91, No. 1, 1987, p. 63-82.

Research output: Contribution to journalArticle

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abstract = "Optical excitation and emission spectra are reported for Na aluminosilicate glassed doped with 0.001-0.005 M Tl+ ions, whose spectra probe Na+ environments in the glasses. The experimental data buttress earlier work by the authors, which showed that Al/Na = 1 is the condition for (dis)appearance of nonbridging oxygens in Na aluminosilicate glasses. The Tl+ spectra are in qualitative disagreement with theories of average optical basicity propounded by J{\o}rgensen and by Duffy and Ingram (glass compositions were chosen so samples had theoretical optical basicities of Λth = 0.55, 0.57, or 0.60). In contrast to the single absorption band predicted by average basicity theories, two absorption bands were found for Tl+ in Na aluminosilicate glasses. The two bands arise from Tl+ acting as network modifiers and from Tl+ acting as charge compensators for network Al. The principal features of these spectra are shown to be consistent with XPS results. The assumptions underlying average and group optical basicity theories are critically reviewed and are found to be deficient in that: (1) they direct attention to a network atom (Si or Al) and the oxygen bonded to it, rather than to the luminescent probe ion and its neighboring oxygens; (2) they neglect lattice relaxation (Franck-Condon shift) effects. Important special circumstances are nevertheless identified in which average optical basicity theories may be useful guides to the peak energies of probe ion spectra.",
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